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At least 937 records · Page 52

Charge Delocalization and Vibronic Couplings in Quadrupolar Squaraine Dyes

Squaraines are prototypical quadrupolar charge-transfer chromophores that have recently attracted much attention as building blocks for solution-processed photovoltaics, fluorescent probes with large two-photon absorption cross sections, and aggregates with large circular dichroism. Their optical properties are often rationalized in terms of phenomenological essential state models, considering the coupling of two zwitterionic excited states to a neutral ground state. As a result, optical transitions to the lowest S 1 excited state are one-photon allowed, whereas the next higher S 2 state can only be accessed by two-photon transitions. A further implication of these models is a substantial reduction of vibronic coupling to the ubiquitous high-frequency vinyl-stretching modes of organic materials. Here, in this study, we combine time-resolved vibrational spectroscopy, two-dimensional electronic spectroscopy, and quantum-chemical simulations to test and rationalize these predictions for nonaggregated molecules. We find small Huang–Rhys factors below 0.01 for the high-frequency, 1500 cm –1 modes in particular, as well as a noticeable reduction for those of lower frequency modes in general for the electronic S 0 → S 1 transition. The two-photon allowed state S 2 is well separated energetically from S 1 and has weak vibronic signatures as well. Thus, the resulting pronounced concentration of the oscillator strength in a narrow region relevant to the lowest electronic transition makes squaraines and their aggregates exceptionally interesting for strong and ultrastrong coupling of excitons to localized light modes in external resonators with chiral properties that can largely be controlled by the molecular architecture.

36 MATERIALS SCIENCE↗

"Dust Devils": Gardening Agents on the Surface of Mars, and Hidden Hazards to Human Exploration?

Dust devils are familiar sites in the and regions of the world: they can produce quite spectacular displays of dust lofting when the vortices scavenge very loose dust from a dry lake bed or from recently disturbed agricultural fields. If one were to arrive at the center of an arid region, take one photograph, or even a series of photographs over a period of several days, then return the images for laboratory analysis, it would be most likely concluded that the region was inactive from an aeolian perspective. No images of general dust movement were obtained, nor were any dust devils "caught on camera" owing to their ephemeral and unpredictable appearance, and the fact that there was deceptively little residue of their actions. If, however, a camera were to take a 360 degree continuous recording over a period of a year, and the film were then to be shown at high speed over a period a several minutes, the impression might be that of a region ravaged by air vorticity and dust movement. Extrapolate this over geological time, and it is possible to visualize dust devils as prime aeolian agents, rather than insignificant vagaries of nature, On Mars, the thin atmosphere permits the surface of the planet to be heated but it does not itself retain heat with the capacity of the earth's atmosphere. This gives rise to greater thermal instability near the surface of Mars as "warm" air pockets diapiritically inject themselves into higher atmospheric layers. Resulting boundary-layer vorticity on Mars might therefore be expected to produce dust devils in abundance, if only seasonally. The spectacular images of dust devils obtained by Pathfinder within its brief functional period on the planet testify to the probability of highly frequent surface vorticity in light of the above reasoning about observational probability. Notably, the Pathfinder devils appeared to be at least a kilometer in height. There are several consequences for the geology of Mars, and for human exploration, if dust devils are to be expected in reasonable abundance. First, from a geological perspective, the vortices will act as "gardening" agents for the top few centimeters of entrainable material. Over time (hundreds of millions, or billions of years being available), they will cover the surface with scouring paths, and the grain sizes that can be lofted by a vortex probably extends over the whole sand to dust range. The depositional paths are, of course, much larger, so that vortex-induced deposition is more widespread than vortex-induced erosion, and will without doubt, affect the whole region in which the dust devils occur (this might explain why rocks at the Viking site seemed oddly capped with dust in a region apparently subject to general aeolian scouring). On Mars, the lift forces in dust devils might be less than on earth owing to the much thinner atmosphere, but this may be counterbalanced by lower gravity and greater vortex velocities. Certainly, when active, other aeolian phenomena on Mars --sand motion and dust storms, seem no less energetic and no less capable of lofting sediments than equivalent terrestrial aeolian phenomena. Every several years, within the current climatic regime, the surface of Mars is subject to light dust fall from global dust storms. Over time, this should develop a very uniform surface layer, with commensurate uniformity in grain size, mineralogy, albedo, color, and general spectroscopic properties. Dust devils will disturb this situation by continually mixing the surface dust with underlying layers, perhaps composed of silt and sand. This size mixing will also involve compositional mixing. After some years, the thin layer of dust that may be difficult to entrain alone, becomes progressively mixed with coarser materials that could reduce the general aeolian threshold of the soil. Certainly the continual disturbance by vorticity will prevent surface stabilization that may bind or indurate grains (caused by slow cementation or ice welding at grain boundaries). If dust devils continually loft dust to kilometer heights, and the dust is sprayed into many cubic kilometers of atmosphere each time, could the devils produce a continual background of atmospheric dust that might be mistaken for the fallout of a distant large-scale dust storm? From a human exploration perspective, dust devils are unlikely to pose any, life- threatening situation for an astronaut unfortunate enough to encounter a momentary swirling cloud of loose soil. However, it is noted that pervasive dust is probably one of the greatest long-term hazards for a human encampment. The fineness and penetration capabilities of the dust, its electrostatic adhesive properties, and its complete ubiquity, render the material a persistent nuisance at best, but at worst, over a period of many months it is possible that space suits, machinery, habitat interiors, air filters, and so forth, could become jeopardized. Owing to dust penetration, the space suits used in the Apollo landings were rendered unusable after a few EVA activities. There will be a definite attempt to situate a human colony on Mars in an area that is far removed from the regions of the planet known for being the centers of major dust storms. At the heart of these storm systems, the dust lofting mechanics are unknown, but they are energetic and perhaps potentially life-threatening for an astronaut. Locating a colony in a region that appears from space to be meteorologically benign may lead to colony placement in a region prone to dust devils, but dust devils are not (or have not been) detectable from orbital observations: the region surveyed for placement will appear like the apparently inactive and area referred to earlier. The region may be spared from highly energetic weather systems, but it may not be necessarily immune from continual dust disturbance. Additional information is contained in the original.

Marshall, J.↗

Electrostatic Superlattices Beyond 1:1 Stoichiometry

ABSTRACT Exotic nanoparticle superstructures can be accessed by harnessing nanoparticle softness and charge regulation, features often viewed as obstacles to structural control. Here, we show that regulated charge mismatch in polymer‐grafted nanoparticles enables the assembly of high‐stoichiometry cubic superlattices. By co‐tuning grafting density, particle size, and bulk composition, we realize ionic‐lattice analogues, such as and , as well as single‐component and superlattices without atomic counterparts. The superlattice has recently been identified theoretically as a photonic band‐gap lattice. These phases emerge from a 1:1 “parent” lattice when local charge neutrality cannot be satisfied, driving either progressive interstitial filling or reorganization into a larger basis. For instance, the systematic occupation of ZnS tetrahedral sites yields , while ligand‐swapping symmetry breaking converts CsCl into . Upon heating, the assemblies exhibit reversible lattice contraction and pronounced negative thermal expansion. Furthermore, the energetic penalty for defects increases with nanoparticle size, facilitating the scalable production of high‐quality, open superlattices for photonic applications.

36 MATERIALS SCIENCE↗

Vacancy surface migration mechanisms in dilute nickel-chromium alloys

We investigate the unitary mechanisms related to the surface migration of vacancies in dilute Ni-Cr alloys via first-principle calculations. We survey a complete set of surface and sub-surface migration paths for vacancies near the (100) free surface and calculate the corresponding migration barriers. Our results show that a vacancy migrating towards the free surface will face lower energy barriers to migrate via atomic exchange with a neighboring Cr atom rather than with a Ni atom. Once a vacancy reaches the free surface, it will be trapped there. Our results also reveal that, when a Cr atom sits in the atomic plane just below the free surface, any in-plane vacancy hopping jump that would result in the vacancy sitting on top a subsurface Cr atom is energetically unfavorable. Taken together, these fundamental unitary surface migration mechanisms offer insights into the complex interactions between surface segregation and vacancy migration phenomena in Ni-Cr-based alloys.

36 MATERIALS SCIENCE↗

Workhorse minimally empirical dispersion-corrected density functional with tests for weakly bound systems: r 2 SCAN + rVV 10

SCAN+rVV10 has been demonstrated to be a versatile van der Waals (vdW) density functional that delivers good predictions of both energetic and structural properties for many types of bonding. Recently, the r 2 SCAN functional was devised as a revised form of SCAN with improved numerical stability. In this work, we refit the rVV10 functional to optimize the r 2 SCAN+rVV10 vdW density functional and test its performance for molecular interactions and layered materials. Our molecular tests demonstrate that r 2 SCAN+rVV10 outperforms its predecessor SCAN+rVV10 in both efficiency (numerical stability) and accuracy. This good performance is also found in lattice-constant predictions. In comparison with benchmark results from higher-level theories or experiments, r 2 SCAN+rVV10 yields excellent interlayer binding energies and phonon dispersions for layered materials.

36 MATERIALS SCIENCE↗

Shock-wave properties and high-pressure equations of state of geophysically important materials

Shock wave (Hugoniot), shock temperature, and release data are presented for several geophysically important, refractory materials. A sensitive multichannel optical pyrometer was developed to measure shock temperatures (2500 to 5600 K at pressures from 48 to 117 GPa) in anorthite (CaAl2Si2O8) glass. Shock temperatures of 3750 to 6000 K at pressures from 140 to 182 GPa were measured in calcium oxide (CaO). Temperature data were used to constrain the energetics of the B1-B2 phase transition at 70 GPa in CaO, and to construct a finite strain equation of state for CaO consistent with previous Hugoniot data. The CaO equation of state was used with equation of state parameters of other oxides to construct a theoretical mixed oxide Hugoniot of anorthite, which is in agreement with new Hugoniot data above about 50 GPa, determined using experimental techniques developed. The mixed oxide model, however, overestimates the shock temperatures, and does not accurately predict measured release paths.

Boslough, M. B.↗

Atomic structures of interfacial solute gateways to θ' precipitates in Al-Cu alloys

Many materials employed in critical structural applications depend upon metastable strengthening precipitates that transform or dissolve at elevated temperatures. Herein, aberration-corrected scanning transmission electron microscopy and first-principles calculations are used to accurately determine the atomic structure of the highly mobile, semi-coherent precipitate interfaces that control this process in the classic θ' (Al 2 Cu) precipitate in the Al-Cu system. Semi-coherent {110} interfaces are found to be composed of an array of unexpected misfit dislocations that are arranged in two different structural units. Dislocations accommodate nearly all of the misfit between the Al matrix and strengthening phase. Cu is observed to segregate to the compressed edge of the dislocation cores at specific sites in this interface. First-principles calculations revealed the energetic landscape that facilitates these sites to become entry and exit gateways of Cu atoms in this semi-coherent interface. In conclusion, this investigation reveals critical features within semi-coherent interfaces that determine the thermal stability of precipitation-hardened alloys.

36 MATERIALS SCIENCE↗

Epitaxial growth of hexagonal BaNi O 3–δ thin films on SrTi O 3 (111) substrates

Transition metal oxides containing nickel species in oxidation states higher than 3+ often exhibit high catalytic activity, which makes them promising for applications as advanced electrocatalysts for water splitting and fuel cells. Here, we examine the structure and properties of BaNiO 3 (BNO) thin films, containing formally Ni 4+ , grown on SrTiO 3 (111) substrates using oxygen-plasma–assisted molecular beam epitaxy. X-ray diffraction and scanning transmission electron microscopy measurements reveal that BNO films have a hexagonal structure with $c$- and $a$-axes of mixed textures showing epitaxial relationships BNO (0001) ∥ SrTiO 3 (111) and BNO (10$\overline{1}$0) ∥ SrTi O 3 (111), respectively. The formation of the $a$-axis texture is dominant due to the smaller lattice mismatch with the substrate. Here, density functional theory calculations confirm that the hexagonal BNO film with the $a$-axis texture is energetically more favorable than the competing $c$-axis texture. Detailed spectroscopy data analysis indicates that hexagonal BNO films contain mixtures of Ni 2+ , Ni 3+ , and Ni 4+ species, with Ni 4+ being dominant. Our study provides insights into stabilizing Ni 4+ in complex oxides, which is important for further exploration of the potential of materials containing Ni 4+ .

36 MATERIALS SCIENCE↗

Two-dimensional electron beam charging model for polymer films

A two-dimensional model is developed to describe the charging of strips of thin polymer films above a grounded substrate exposed to a uniform mono-energetic electron beam. The study is motivated by the observed anomalous behavior of geosynchronous satellites, which has been attributed to differential charging of the satellite surfaces exposed to magnetospheric electrons. Surface and bulk electric fields are calcuated at steady state in order to identify regions of high electrical stress, with emphasis on behavior near the material's edge. The model is used to study the effects of some of the experimental parameters, notably beam energy, beam angle of incidence, beam current density, material thickness and material width. Also examined are the consequences of a central gap in the material and a discontinuity in the material thickness.

Reeves, R. D.↗

Galactic Cosmic Ray Event-Based Risk Model (GERM) Code

This software describes the transport and energy deposition of the passage of galactic cosmic rays in astronaut tissues during space travel, or heavy ion beams in patients in cancer therapy. Space radiation risk is a probability distribution, and time-dependent biological events must be accounted for physical description of space radiation transport in tissues and cells. A stochastic model can calculate the probability density directly without unverified assumptions about shape of probability density function. The prior art of transport codes calculates the average flux and dose of particles behind spacecraft and tissue shielding. Because of the signaling times for activation and relaxation in the cell and tissue, transport code must describe temporal and microspatial density of functions to correlate DNA and oxidative damage with non-targeted effects of signals, bystander, etc. These are absolutely ignored or impossible in the prior art. The GERM code provides scientists data interpretation of experiments; modeling of beam line, shielding of target samples, and sample holders; and estimation of basic physical and biological outputs of their experiments. For mono-energetic ion beams, basic physical and biological properties are calculated for a selected ion type, such as kinetic energy, mass, charge number, absorbed dose, or fluence. Evaluated quantities are linear energy transfer (LET), range (R), absorption and fragmentation cross-sections, and the probability of nuclear interactions after 1 or 5 cm of water equivalent material. In addition, a set of biophysical properties is evaluated, such as the Poisson distribution for a specified cellular area, cell survival curves, and DNA damage yields per cell. Also, the GERM code calculates the radiation transport of the beam line for either a fixed number of user-specified depths or at multiple positions along the Bragg curve of the particle in a selected material. The GERM code makes the numerical estimates of basic physical and biophysical quantities of high-energy protons and heavy ions that have been studied at the NASA Space Radiation Laboratory (NSRL) for the purpose of simulating space radiation biological effects. In the first option, properties of monoenergetic beams are treated. In the second option, the transport of beams in different materials is treated. Similar biophysical properties as in the first option are evaluated for the primary ion and its secondary particles. Additional properties related to the nuclear fragmentation of the beam are evaluated. The GERM code is a computationally efficient Monte-Carlo heavy-ion-beam model. It includes accurate models of LET, range, residual energy, and straggling, and the quantum multiple scattering fragmentation (QMSGRG) nuclear database.

Cucinotta, Francis A.↗

Bonds over Electrons: Proton Coupled Electron Transfer at Solid–Solution Interfaces

This Perspective argues that most redox reactions of materials at an interface with a protic solution involve net proton-coupled electron transfer (PCET) (or other cation-coupled ET). This view contrasts with the traditional electron-transferfocused view of redox reactions at semiconductors, but redox processes at metal surfaces are often described as PCET. Taking a thermodynamic perspective, transfer of an electron is typically accompanied by a stoichiometric proton, much as the chemistry of lithium-ion batteries involves coupled transfers of e – and Li + . The PCET viewpoint implicates the surface–H bond dissociation free energy (BDFE) as the preeminent energetic parameter and its conceptual equivalents, the electrochemical ne – /nH + potential versus the reversible hydrogen electrode (RHE) and the free energy of hydrogenation, ΔG° H . These parameters capture the thermochemistry of PCET at interfaces better than electronic parameters such as Fermi energies, electron chemical potentials, flatband potentials, or band-edge energies. A unified picture of PCET at metal and semiconductor surfaces is presented. Exceptions, limitations, implications, and future directions motivated by this approach are described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Implications of the fractional charge of hydroxide at the electrochemical interface

Rational design of materials that efficiently convert electrical energy into chemical bonds will ultimately depend on a thorough understanding of the electrochemical interface at the atomic level. Towards this goal, the use of density functional theory (DFT) at the generalized gradient approximation (GGA) level has been applied widely in the past 15 years. In the calculation of electrochemical reaction energetics using GGA-DFT, it is frequently implicitly assumed that ions in the Helmholtz plane have unit charge. However, the ion charge is observed to be fractional near the interface through both a capacitor model and through Bader charge partitioning. In this work, we show that this spurious charge transfer can be effectively mitigated by continuum charging of the electrolyte. Finally, we show that, similar to hydronium, the observed fractional charge of hydroxide is not due to a GGA level self-interaction error, as the partial charge is observed even when using hybrid level exchange–correlation functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Stuff of Other Worlds

Extraterrestrial material eternally rains down on Earth. Meteorites flare in the night sky. Cosmic rays plow into Earth's atmosphere, creating invisible bursts of secondary particles. These processes began when the Earth formed in the primordial solar system and have continued ever since, indifferent to the exceedingly recent presence of human intelligence. For us to seek out stuff of other worlds, in contrast, takes a great deal of determined ingenuity. First we have to send a spacecraft somewhere else in the solar system. Indigenous material has to be collected and then brought back to Earth without exposure to conditions that might significantly alter it. The material must undergo meaningful scientific analysis. Most important, part of the material is preserved intact for future investigations. Beginning with bringing back Moon rocks, and now moving onward in the form of new missions to capture the hot thin solar wind and cold thin atmosphere of comets, extraterrestrial sample return takes place on the cutting edge of scientific technology. Sample return is also the fulcrum of an energetic debate about how to do planetary science missions. Scientists and engineers are debating whether to rely on remote sensing and in situ analysis, or to plan missions to undertake sample return. The latter is definitely more expensive on a per mission basis, and is usually technologically more challenging. But for an initially high investment of money and technology, bringing the stuff of other worlds back to Earth yields an incomparable return in scientific results.

Stansbery, EIleen K.↗

Computational design of thermoelectric alloys through optimization of transport and dopability

Alloying is a common technique to optimize the functional properties of materials for thermoelectrics, photovoltaics, energy storage etc. Designing thermoelectric (TE) alloys is especially challenging because it is a multi-property optimization problem, where the properties that contribute to high TE performance are interdependent. In this work, we develop a computational framework that combines first-principles calculations with alloy and point defect modeling to identify alloy compositions that optimize the electronic, thermal, and defect properties. We apply this framework to design n-type Ba 2(1–x) Sr 2x CdP 2 Zintl thermoelectric alloys. Our predictions of the crystallographic properties such as lattice parameters and site disorder are validated with experiments. To optimize the conduction band electronic structure, we perform band unfolding to sketch the effective band structures of alloys and find a range of compositions that facilitate band convergence and minimize alloy scattering of electrons. Here, we assess the n-type dopability of the alloys by extending the standard approach for computing point defect energetics in ordered structures. Through the application of this framework, we identify an optimal alloy composition range with the desired electronic and thermal transport properties, and n-type dopability. Such a computational framework can also be used to design alloys for other functional applications beyond TE.

36 MATERIALS SCIENCE↗

Topologically derived dislocation theory for twist and stretch moiré superlattices in bilayer graphene

In this work, we develop a continuum dislocation description of twist and stretch moiré superlattices in two-dimensional material bilayers. The continuum formulation is based on the topological constraints introduced by the periodic dislocation network associated with the moiré structure. The approach is based on solving analytically for the structural distortion and displacement fields that satisfy the topological constraints and that minimize the total energy. The total energy is described by both the strain energy of each individual distorted layer and a Peierls-Nabarro-like interfacial contribution arising from stacking disregistry. The dislocation core emerges naturally within the formalism as a result of the competition between the two contributions. The approach presented here captures the structure and energetics of twist and stretch moiré superlattices of dislocations with arbitrary direction and character, without assuming an analytical solution a priori and while accounting naturally for dislocation-dislocation image interactions. In comparisons to atomistic simulations using classical potentials, the maximum structure deviation is 6%, while the maximum line energy deviation is 0.019 eV/Å. Several applications of our model are shown, including predicting the variation of structure with twist angle and describing dislocation line tension and junction energies.

36 MATERIALS SCIENCE↗

Response of TlCl /I,Be/ crystals to energetic ionizing radiation.

The response of a 3.8-cm TlCl(I,Be) crystal to 8 GeV negative pions is reported. A comparison is also made with the response of a similar CsI(Tl) crystal to the same incident radiation. In addition, the pulse shape and resolution characteristics of a 7.6-cm TlCl(I,Be) crystal, excited by positrons in the energy range 50 to 130 MeV, are reviewed. It is concluded that thallous chloride shows promise of being an excellent scintillating material for the detection and energy determination of high energy photons and charged particles.

Farukhi, M. R.↗

Chapter 5: Mechanical metamaterials and topological soft matter: allostery and auxetics--distributed energetics and mutation upon deployment

At the suggestion of NASA’s Physical Science Research Program in the Space Life and Physical Science Research and Application Division, Paul Chaikin, Noel Clark, and Sidney Nagel organized a focus session and workshop for the 2020 American Physical Society (APS) March meeting under the auspices of the Division of Soft Matter. Three overarching themes emerged from the workshop and are presented with additional details: • Machines made out of machines • Scalable self-sustaining ecosystems • Active materials and metamaterials This report lays out only some of the potential directions for soft matter dynamics over the next two decades. It also lays out the role that gravity plays in the organization of the basic building blocks of matter. Not only will research on soft matter have tremendous application towards understanding its behavior in our terrestrial environment, but also potentially in other NASA programs such as planetary science, exploration, robotics, etc. Attached is a White Paper for the Decadal Survey that consists of an extended Title along with the previous Introduction and Chapter 2.5 from NASA/CP-20205010493.

Soft matter↗